Tetrazoimino compounds



Patented Sept. 29, 1936 UNITED STATES 2,055,547 f TETRAZOIMINO COMPOUNDS Eugene A. Markush, Jersey City, N. 1., assignor to Pharrna Chemical Corporation, New York, N. Y., a corporation of New York No Drawing. Application August 8, 1933 Serial No. 684,178 V 1 p Claims. (Cl. 260-461) My invention relates to the production of stabilized tetrazoimino compounds of the general type in which R is the residue of any diazotizable aromatic amine and is the residue of a heterocyclic cyclization product containing a solubilizing group, or groups,

my tetrazoimino compound and then with a coupling compound followed by an acid treatment. I give the following as examples of my invention, a

Example 1 .5

157 parts 4-chlor-2-amino-anisol are suspended in 400 parts water and 270 parts hydrochloric acid 20' B. Ice is added, if necessary, until the suspension is cooled to about 5 (3., and the mixture diazotized with 70 grs. sodium nitrite dissolved in 350 parts water. The clear diazonium solution is run slowly into a solution of 200 parts soda ash and 214 parts of the hydrolized cyclizasuch as the carboxylic or the sulfonic group. tion P preparefi .from alpha'chlqr"acetyl' 15 I have found that compounds of the described fifammo'cmrilamlc mtnle and alcohohc potas' character possess excellent stability when'sub hydroxlde (Ber' Chem- Gesen" jected to ordinary storage conditions, but which are readily split up into the original diazo body h tetrazolmmo compound W F' Du or bodies and the original cyclization product readfly Fw beicontpletely preclpltated by 20 when Subjected to an acid treatment the addition of salt. It s then filtered, pressed These new compounds, therefore, are valuable and i The t compmtnd thus for the production of dyeings, prints or colored j 1S Prowmsh yellow crystanme i effects upon textile fibers orfabrics, or for the i Soluble m t i when treatec? production Of Such dyes, printing compounds or acid is decomposed into diaz l-chlor-amsidlne 25 colors in substance apart from the textile fibers and the free acld, of the cychzatlon body- Its or fabrics probable formula is:-

In preparing the dyes, printing, compounds or colors in substance apart from textile fibers or so fabrics, the tetrazoimino compounds of my invention may be mixed with a coupling compound capable of combining with the original diazo I (BOOK compound, the mixture treated with acid and the 0:0 3 combination effected by proper means, or the tetrazoimino compounds may be first treated with acid and the diazo-compounds thereof combined cflco with a coupling compound. 0011: C--C-COOH In employing the tetrazoimino compounds of O1 OCHa 40 my invention the textile fiber, or fabric may be g O 40 treated with a mixture of my compounds with a N coupling compound capable of combining with I the original diazo compounds and the thus treat- (31 ed fiber or fabric subjected to the action of an Emmple 2 acid, or the fiber may be first treated with the i V 45 coupling compound and then with my tetrazo- 114 parts of the catalytic reduction product imino compound and subjected to acid treatment, of the double gamma amino acid cyclization body or the fiber, or fabric, may be first treated with (Ber. Chem. Gesell. 35, 4124) IzIH-CH CH-COOH 50 l catalytic COOH-CH NH reduction /NH CH; JE( :H-OOOH 55 CH CH! NH HOH.COON8 Example 3 By replacing the diazonium solution of 185 parts o-amino-diphenyl ether with a molecular equivalent of o-amino-phenyl-benzyl-ether and proceeding as described in Example 2, a tetrazoimino compound is obtained whose probable formula is:-

Among the amines suitable in the following of my invention are the diazotizable amines of the benzene, naphthalene and anthracene series, their esters, ethers and substituted compounds.

I do not limit myself to the particular compounds, quantities or steps of procedure mentioned as these are given simply as a means for clearly describing my invention.

What I claim is:- 1. A tetrazoimino compound having the general formula RN=N in which R and R represent the same or difierent diazotized aromatic amine residues, X represents a dicyclic radical each ring of which consists of 4 carbon atoms and one imino nitrogen atom containing at least one solubilizing member of the group consisting of carboxylic and sulfonic groups the diazo groups being attached to the nuclear nitrogens of the dicyclic radical which compound is split into its original diazotized compound or compounds, and the free heterocyclic diimine upon acid treatment.

2. A tetrazoimino compound producible by combining two molecular proportions of a diazotized aromatic amine with one molecular proportion of a heterocyclic diimine containing at least one solubilizing member of the group consisting of carboxylic and sulfonic groups the diazo groups being attached to the nuclear nitrogens of the dicyclic radical, which compound is split up into its original diazotized compound and. the free acid of the heterocyclic diimine compound upon acid treatment.

3. The tetrazoimino compound producible by combining two molecular proportions of diazotized 4-chl0r-2-amino-anisol with one molecular proportion of a heterocyclic diimine in which each ring consists of 4 carbon atoms and one imino nitrogen atom containing at least one solubilizing member of the group consisting of carboxylic and sulfonic groups the diazo groups being attached to the nuclear nitrogens of the dicyclic radical, which compound is split up into 2-diazo4-chlor-anisidine and the heterocyclic diimine upon acid treatment.

4. The tetrazoimino compound producible by combining two molecular proportions of a diazotized aromatic amine with one molecular proportion of the heterocyclic diimine producible from alpha chlor-acetyl-beta-amino cinnamic nitrile with alcoholic potassium hydroxide which compound is split up into the original diazotized aromatic amine and the heterocyclic diimine upon acid treatment.

5. The tetrazoimino compound producible by combining two molecular proportions of diazotized 4-chlor-2-amino-anisol with one molecular proportion of the heterocyclic diimine producible from alpha-chlor-acetyl-beta-amino cinnamic nitrile with alcoholic potassium hydroxide which compound is split up into 2-diazo-4-chlor-anisidine and the heterocyclic diimine upon acid treatment.

EUGENE A. MARKUSH. 

